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WO2018004250A1 - Matériau actif d'électrode positive pour batterie secondaire au lithium, contenant de l'oxyde de cobalt et de lithium haute tension ayant un élément dopant, et son procédé de préparation - Google Patents

Matériau actif d'électrode positive pour batterie secondaire au lithium, contenant de l'oxyde de cobalt et de lithium haute tension ayant un élément dopant, et son procédé de préparation Download PDF

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WO2018004250A1
WO2018004250A1 PCT/KR2017/006823 KR2017006823W WO2018004250A1 WO 2018004250 A1 WO2018004250 A1 WO 2018004250A1 KR 2017006823 W KR2017006823 W KR 2017006823W WO 2018004250 A1 WO2018004250 A1 WO 2018004250A1
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WIPO (PCT)
Prior art keywords
active material
positive electrode
electrode active
cobalt oxide
lithium
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PCT/KR2017/006823
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English (en)
Korean (ko)
Inventor
조치호
이보람
박성빈
허혁
박영욱
정왕모
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority claimed from KR1020170081193A external-priority patent/KR102095930B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201780003576.5A priority Critical patent/CN108140821B/zh
Priority to PL17820526T priority patent/PL3340348T3/pl
Priority to EP17820526.6A priority patent/EP3340348B1/fr
Priority to US15/765,402 priority patent/US10930931B2/en
Publication of WO2018004250A1 publication Critical patent/WO2018004250A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a cathode active material for a lithium secondary battery including a high voltage lithium cobalt oxide having a doping element and a method of manufacturing the same.
  • lithium secondary batteries have high energy density and operating potential, have long cycle life, and have low self discharge rate. Is commercially available and widely used.
  • LiCoO 2 LiCoO 2
  • Samsung SDI NMC / NCA
  • LiMnO 4 LiFePO 4
  • LiCoO 2 the price of cobalt is high and the capacity of the same voltage is lower than that of the Samsung division, and thus the usage of the Samsung division is gradually increasing to increase the capacity of the secondary battery.
  • LiCoO 2 is excellent in various physical properties such as high rolling density, and excellent in electrochemical properties such as high cycle characteristics.
  • LiCoO 2 has a low charge / discharge current of about 150 mAh / g, a problem of deterioration in life characteristics due to unstable crystal structure at voltages of 4.3 V and higher, and risk of ignition by reaction with electrolyte. have.
  • the energy capacity of the active material is greatly reduced to decrease battery performance, and further, the total content and doping amount of the metal elements included in the active material. And the properties vary depending on the amount of coating not only significantly affects the battery performance, but also has a problem that it is difficult to set the proper range because the high contact durability is greatly changed.
  • the present invention aims to solve the problems of the prior art as described above and the technical problems that have been requested from the past.
  • the inventors of the present application have described the content of element A in the coating layer formed on the surface of a particle in a lithium cobalt oxide including a coating layer and a substitution element formed on the surface of a particle, as described later.
  • the content of element B in the dopant is relatively higher, it was confirmed that the desired effect can be achieved, and the present invention was completed.
  • the element A and the element B are each independently at least one or more selected from the group consisting of Al, Ti, Mg, Zr, Ba, Ca, Ta, Nb, and Mo,
  • the molar ratio of element A in the coating layer: element B in the dopant is greater than 1: 1 and 10: 1 or less.
  • step (b) mixing the lithium cobalt oxide of the step (a) with a compound including the element A, and then firing the material in a secondary manner, thereby providing a method of manufacturing a cathode active material for a secondary battery.
  • a positive electrode which is prepared by applying a slurry containing the positive electrode active material, a conductive material, and a binder for a secondary battery to a current collector, and
  • It provides a lithium secondary battery comprising the positive electrode, the negative electrode, and the electrolyte.
  • the positive electrode active material according to the present invention forms the coating layer containing the metal element A on the surface of the particles of lithium cobalt oxide, while doping the metal element B in the lithium cobalt oxide, the content of the element A in the coating layer of the element B in the dopant Specifically, the molar ratio of element A: element B is greater than 1: 1 to 10: 1 or less so that the amount of element A and element B contained in an appropriate ratio in the dopant and the coating layer is 4.4 V or more.
  • FIG. 1 is a graph showing the capacity retention rate of a battery according to a cycle of a lithium secondary battery including the cathode active materials prepared in Examples 1 to 3 and Comparative Examples 1 to 3.
  • the cathode active material particles for secondary batteries according to the present invention lithium cobalt oxide
  • a coating layer comprising element A formed on the surface of the particles of lithium cobalt oxide
  • the element A and the element B are each independently at least one or more selected from the group consisting of Al, Ti, Mg, Zr, Ba, Ca, Ta, Nb, and Mo,
  • the molar ratio of Element A in the coating layer: Element B in the dopant is greater than 1: 1 and 10: 1 or less.
  • lithium cobalt oxide when used at a high voltage as a cathode active material, a large amount of lithium ions are released from lithium cobalt oxide particles, resulting in a loss of crystal structure, and thus, an unstable crystal structure is collapsed and reversibility is lowered.
  • the lithium ions are Co 3 + or Co 4 + ions in the lithium cobalt oxide particle surface in the released state is to be reduced by the electrolyte, the oxygen is desorbed from the crystal structure of the above-described structure, the collapse is further promoted.
  • a coating layer containing a metal is formed on the particle surface of lithium cobalt oxide, and while the metal is doped in the lithium cobalt oxide, the content of element A in the coating layer is relatively higher than that of element B in the dopant.
  • the dopant may be preferentially oxidized over cobalt (Co) at a charge condition of 4.4 V or more to provide structural stability, and the coating layer may provide stability of particle surfaces of lithium cobalt oxide.
  • the lithium cobalt oxide may have a composition of the formula (1).
  • M and Me are at least one selected from the group consisting of Al, Ti, Mg, Zr, Ba, Ca, Ta, Nb, and Mo;
  • the lithium cobalt oxide may have a composition of Formula 2 including a thin film of lithium excess on the surface.
  • M and Me are each independently at least one selected from the group consisting of Al, Ti, Mg, Zr, Ba, Ca, Ta, Nb, and Mo;
  • M and Me are doping element B.
  • the element B may be at least one or more selected from the group consisting of Al, Mg, Zr and Ti, in detail may be at least one or more selected from the group consisting of Al, Mg and Ti, more specifically Mg And Ti.
  • the lithium cobalt-based oxide having the composition of Formula 1 in detail, LiCo 0 . 998 Mg 0 . 001 Ti 0 . 001 0 2 , LiCo 0 . 995 Mg 0. 002 Al 0 . 003 O 2, LiCo 0. 999 Mg 0 . 001 O 2 , LiCo 0.996 Mg 0.002 Ti 0.002 O 2 , LiCo 0 . 997 Mg 0 . 002 Al 0 . 001 O 2 , or LiCo 0 . 996 Mg 0 . 002 Ti 0 . 001 Al 0 .
  • the lithium cobalt oxide having a composition of the formula (II), particularly, Li 0.05 (LiCo 0.998 Mg 0.001 Ti 0.001 O 2), Li 0 .1 (LiCo 0. 995 Mg 0. 002 Al 0. 003 O 2), Li 0 .02 (LiCo 0. 999 Mg 0. 001 O 2), Li 0.06 (LiCo 0.996 Mg 0.002 Ti 0.002 O 2), Li 0 .08 (LiCo 0. 997 Mg 0. 002 Al 0. 001 may be a O 2), or Li 0.09 (LiCo 0.996 Mg 0.002 Ti 0.001 Al 0.001 O 2).
  • Li 0.05 LiCo 0.998 Mg 0.001 Ti 0.001 O 2
  • Li 0 .1 LiCo 0. 995 Mg 0. 002 Al 0. 003 O 2
  • Li 0 .02 LiCo 0. 999 Mg 0. 001 O 2
  • the coating element A may be at least one or more selected from the group consisting of Al, Mg, Zr, and Ti, and specifically Mg and Ti.
  • the coating layer including the element A may be formed by firing, and specifically, Al 3 O 4 , ZrO 2 , Al (OH), Mg (OH) 2 , Al 2 O 3 , MgO, ZrO, Li 2 It may include at least one selected from the group consisting of ZrO 3 and TiO 2 .
  • the elements A and B may be the same element.
  • the elements A and B are the same, excellent results can be obtained in terms of both the doping effect and the coating effect.
  • the contribution to the structural stability due to the element B in the dopant is large, it can be said that there is an excellent effect on the surface stability of the coating layer containing the same element A as the element B. Therefore, it is more preferable as compared with containing different elements.
  • the molar ratio of element A in the coating layer to element B in the dopant may be greater than 1: 1 and less than or equal to 10: 1, preferably 1.3: 1 to 5: 1, 1.3: 1 to 3.5: 1, 1.3: 1 to 3.2: 1, 1.3: 1 to 3: 1, more preferably 1.3: 1 to 2.5: 1.
  • the mobility of lithium ions may be reduced due to the excess metal included in the coating layer, resulting in a decrease in output characteristics. Relatively small amounts of lithium cobalt oxide in the same volume may lead to a decrease in capacity.
  • there are too few doping elements there exists a problem that there is little doping effect which raises the structural safety of an active material.
  • the molar ratio of element A in the coating layer to element B in the dopant is 1: 1 or less, the effect of coating cannot be sufficiently exhibited, or the ratio of metal B on the surface of the positive electrode active material particles is too high, so that the positive electrode active material is relatively high. There is a problem that the overall capacity of the can be reduced.
  • the molar ratio of the coating layer is small, as the coating area decreases, corrosion of the surface of the cathode active material is accelerated, resulting in inferior lifetime and storage characteristics.
  • the molar ratio of element A: element B in the dopant in the coating layer may include a sum of heterogeneous elements.
  • the content of the element A in the coating layer may be greater than 0 to 20,000 ppm based on the total weight of the positive electrode active material, in detail, may be 500 to 1,500 ppm, more specifically 700 to 1,000 ppm. .
  • the weight of the element B in the dopant may be greater than 0 to 20,000 ppm based on the total amount of the positive electrode active material, in detail, may be 500 to 1,500 ppm, more specifically may be 700 to 1,000 ppm.
  • the ppm content of the element A is, of course, higher than the ppm content of the element B.
  • the present invention provides a method for manufacturing the positive electrode active material for the secondary battery, the manufacturing method,
  • step (b) mixing the lithium cobalt oxide of step (a) with a compound containing element A and then performing secondary firing;
  • the doping precursor including the element B is mixed in a static amount, and first calcined to produce lithium cobalt oxide particles in which the element B is substituted, and an appropriate amount.
  • a compound including an element A may be coated on the surface of the lithium cobalt oxide particles, and the secondary active material may be prepared by forming a coating layer through a secondary firing process. At this time, the content of the element A in the coating layer is set to be greater than the content of the element B in the dopant.
  • the content of the element A in the coating layer formed on the particle surface of the lithium cobalt oxide is prepared to be relatively higher than the content of the element B in the dopant, and the elements A and B contained in the coating layers in an appropriate ratio are preferentially oxidized over cobalt (Co) under 4.4 V or more of charging conditions, thereby exhibiting the stability of the internal structure of the positive electrode active material particles and the surface structure change of the positive electrode active material.
  • the effect of suppressing the increase in surface safety can serve as an optimal range that can prevent degradation of cycle characteristics of the secondary battery at high voltage.
  • a doping precursor including a lithium precursor, cobalt oxide, and element B is mixed as in step (a).
  • the mixing molar ratio of the lithium precursor (Li), cobalt oxide (Co), and the doping precursor (element B) including the element B may be 0.95: 0.90: 0.001 to 1.10: 1.05: 0.05.
  • the cobalt oxide is not limited in kind, but preferably, at least one selected from the group consisting of Co 3 O 4 , CoCO 3 , Co (NO 3 ) 2 and Co (OH) 2 .
  • the group consisting of Co 3 O 4 , CoCO 3 , Co (NO 3 ) 2 and Co (OH) 2 can be.
  • the lithium precursor is not limited as long as it is a compound containing a lithium source, preferably, at least one selected from the group consisting of Li 2 CO 3 , LiOH, LiNO 3 , CH 3 COOLi and Li 2 (COO) 2 . have.
  • the doping precursor may be at least one selected from the group consisting of metals, metal oxides and metal salts.
  • the metal salt may include, for example, acetate, nitrate, sulfate, etc. of the metal element (B), but is not limited thereto.
  • a mixture of the lithium precursor, the cobalt oxide, and the doping precursor including the element B is first calcined to prepare a spherical lithium cobalt oxide.
  • the primary firing may be performed for 8 hours to 12 hours at 800 °C to 1200 °C.
  • the primary firing may be performed for 8 hours to 12 hours at 800 °C to 1200 °C.
  • doping may not be performed well and the internal structure of the positive electrode active material particles may not be stably formed.
  • the primary firing is performed at a temperature exceeding 1200 ° C., or performed for more than 12 hours, the physical and chemical properties of the lithium cobalt oxide may be changed, thereby causing performance degradation.
  • the compound containing element A forming the coating layer is preferably Al 3 O 4 , ZrO 2 , Al (OH), Mg (OH) 2 , Al 2 O 3 , MgO, ZrO, Li 2 ZrO 3 and TiO It may include at least one selected from the group consisting of 2 , but is not limited thereto.
  • the secondary firing may be performed for 3 hours to 8 hours at 400 °C to 800 °C.
  • the secondary firing when the secondary firing is performed at a temperature of less than 400 ° C., or less than 3 hours, the surface of the cathode active material particles may not be stably formed due to poor coating on the surface of the cathode active material. You may not be able to.
  • the secondary firing when the secondary firing is performed at a temperature exceeding 800 ° C. or more than 8 hours, the physical and chemical properties of the lithium cobalt oxide constituting the positive electrode active material particles are changed, thereby degrading performance. It is not preferable because it can cause.
  • the present invention also provides a cathode prepared by applying a slurry containing the cathode active material for a secondary battery, a conductive material, and a binder to a current collector.
  • the positive electrode may be manufactured by, for example, applying a positive electrode active material composed of the above-mentioned positive electrode active material particles to a positive electrode current collector, and a positive electrode mixture in which a conductive material and a binder are mixed. Further filler may be added to the mixture.
  • the positive electrode current collector is generally manufactured to a thickness of 3 ⁇ 300 ⁇ m, and is not particularly limited as long as it has a high conductivity without causing chemical changes in the battery, for example, stainless steel, aluminum, nickel, titanium , And one selected from surface treated with carbon, nickel, titanium, or silver on the surface of aluminum or stainless steel may be used, and in detail, aluminum may be used.
  • the current collector may form fine irregularities on the surface to increase adhesion of the positive electrode active material, and may be in various forms such as a film, sheet, foil, net, porous body, foam, and nonwoven fabric.
  • the conductive material is typically added in an amount of 0.1 to 30% by weight based on the total weight of the mixture including the positive electrode active material.
  • a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite such as natural graphite and artificial graphite; Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the binder is a component that assists the bonding of the active material and the conductive material to the current collector, and is generally added in an amount of 0.1 to 30 wt% based on the total weight of the mixture including the positive electrode active material.
  • binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene , Polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers, and the like.
  • the present invention also provides a secondary battery comprising the positive electrode, the negative electrode and the electrolyte.
  • the type of the secondary battery is not particularly limited, but as a specific example, the secondary battery may be a lithium secondary battery such as a lithium ion battery, a lithium ion polymer battery, or the like having advantages of high energy density, discharge voltage, output stability, and the like.
  • a lithium secondary battery is composed of a positive electrode, a negative electrode, a separator, and a lithium salt-containing nonaqueous electrolyte.
  • the negative electrode is manufactured by coating and drying a negative electrode active material on a negative electrode current collector, and optionally, the components included in the positive electrode described above may be further included as necessary.
  • the negative electrode current collector is generally made to a thickness of 3 to 500 ⁇ m.
  • the negative electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • a surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper, or stainless steel may be used.
  • Surface-treated with carbon, nickel, titanium, silver and the like, aluminum-cadmium alloy and the like can be used.
  • fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • carbon such as hardly graphitized carbon and graphite type carbon
  • Me: Mn, Fe, Pb, Ge; Me' Metal complex oxides such as Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, halogen, 0 ⁇ x ⁇ 1; 1 ⁇ y ⁇ 3; 1 ⁇ z ⁇ 8); Lithium metal; Lithium alloys; Silicon-based alloys; Tin-based alloys; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , and metal oxides such as Bi 2
  • the separator is interposed between the anode and the cathode, and an insulating thin film having high ion permeability and mechanical strength is used.
  • the pore diameter of the separator is generally from 0.01 to 10 ⁇ m ⁇ m, thickness is generally 5 ⁇ 300 ⁇ m.
  • a separator for example, olefin polymers such as chemical resistance and hydrophobic polypropylene; Sheets or non-woven fabrics made of glass fibers or polyethylene are used.
  • a solid electrolyte such as a polymer
  • the solid electrolyte may also serve as a separator.
  • the said lithium salt containing non-aqueous electrolyte solution consists of a nonaqueous electrolyte solution and a lithium salt.
  • nonaqueous electrolyte nonaqueous organic solvents, organic solid electrolytes, inorganic solid electrolytes, and the like are used, but not limited thereto.
  • non-aqueous organic solvent examples include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, and gamma Butyl lactone, 1,2-dimethoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethylsulfoxide, 1,3-dioxolon, formamide, dimethylformamide, dioxorone , Acetonitrile, nitromethane, methyl formate, methyl acetate, phosphate triester, trimethoxy methane, dioxorone derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbo Aprotic organic solvents such as nate derivatives, tetrahydrofuran derivatives, ethers, methyl pyroionate and ethyl propionate can be used
  • organic solid electrolytes examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, polyedgetion lysine, polyester sulfides, polyvinyl alcohols, polyvinylidene fluorides, Polymers containing ionic dissociating groups and the like can be used.
  • Examples of the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Nitrides, halides, sulfates and the like of Li, such as Li 4 SiO 4 -LiI-LiOH, Li 3 PO 4 -Li 2 S-SiS 2, and the like can be used.
  • the lithium salt is a good material to be dissolved in the non-aqueous electrolyte, for example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium tetraphenyl borate and imide have.
  • pyridine triethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, Nitrobenzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrroles, 2-methoxy ethanol, aluminum trichloride and the like may be added.
  • pyridine triethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide
  • Nitrobenzene derivatives sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyr
  • a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride may be further included, and carbon dioxide gas may be further included to improve high temperature storage characteristics, and FEC (Fluoro-Ethylene) may be further included. Carbonate), PRS (Propene sultone) may be further included.
  • the present invention also provides a battery pack including the secondary battery and a device including the battery pack. Since the battery pack and the device are known in the art, detailed descriptions thereof are omitted herein. do.
  • the device may be, for example, a laptop computer, a netbook, a tablet PC, a mobile phone, an MP3, a wearable electronic device, a power tool, an electric vehicle (EV), or a hybrid electric vehicle (HEV).
  • PHEVs Plug-in hybrid electric vehicles
  • E-bikes electric bikes
  • E-scooters electric golf carts
  • Dry mix of Co 3 O 4 , LiOH, TiO 2 and MgO so that Li: Co: Ti: Mg is 1.0: 0.998: 0.0007: 0.0008, and the content of TiO 2 and MgO is 1000 ppm based on the entire cathode active material after mixing so that, by the first calcined for 10 hours at 1,030 °C furnace to prepare a lithium cobalt oxide, and the prepared in order to form a coating layer in the manufactured lithium cobalt oxide lithium cobalt oxide, TiO 2 and MgO dry After mixing, coating TiO 2 and MgO by dry mixing (coating: doping molar ratio 1.3: 1) to 1300 ppm based on the whole of the positive electrode active material, and then firing it in a furnace for 2 hours at 530 ° C. for 6 hours. Synthesized.
  • the positive electrode active material: binder: conductive material was mixed well in NMP so that the weight ratio was 96: 2: 2, and then 20 ⁇ m. It was applied to a thick Al foil and dried at 130 ° C. to prepare a positive electrode.
  • Lithium cobalt oxide was prepared by adjusting the content of TiO 2 and MgO to 750 ppm based on the entire cathode active material, and the lithium cobalt oxide and TiO 2 and MgO prepared above were dried to 2400 ppm based on the entire cathode active material.
  • Lithium cobalt oxide was prepared by adjusting the content of TiO 2 and MgO to 1200 ppm based on the entire cathode active material, and dry mixing the lithium cobalt oxide prepared above and TiO 2 and MgO to 300 ppm based on the entire cathode active material.

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Abstract

La présente invention concerne des particules de matériau actif d'électrode positive pour une batterie secondaire, les particules comprenant : un oxyde de cobalt et de lithium ; une couche de revêtement formée sur une surface de particule de l'oxyde de cobalt et de lithium et contenant l'élément A ; et un dopant contenant l'élément B substitué dans l'oxyde de cobalt et de lithium, les éléments A et B étant chacun indépendamment au moins un élément choisi dans le groupe constitué par Al, Ti, Mg, Zr, Ba, Ca, Ta, Nb et Mo, et le rapport molaire de l'élément A dans la couche de revêtement à l'élément B dans le dopant étant supérieur à 1:1 et inférieur ou égal à 10:1.
PCT/KR2017/006823 2016-06-28 2017-06-28 Matériau actif d'électrode positive pour batterie secondaire au lithium, contenant de l'oxyde de cobalt et de lithium haute tension ayant un élément dopant, et son procédé de préparation WO2018004250A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201780003576.5A CN108140821B (zh) 2016-06-28 2017-06-28 包含具有掺杂元素的高电压锂钴氧化物的锂二次电池用正极活性材料及其制造方法
PL17820526T PL3340348T3 (pl) 2016-06-28 2017-06-28 Materiał aktywny elektrody dodatniej do litowych baterii akumulatorowych, zawierający wysokonapięciowy tlenek litowo-kobaltowy z pierwiastkiem domieszkującym oraz sposób jego wytwarzania
EP17820526.6A EP3340348B1 (fr) 2016-06-28 2017-06-28 Matériau actif d'électrode positive pour batterie secondaire au lithium, contenant de l'oxyde de cobalt et de lithium haute tension ayant un élément dopant, et son procédé de préparation
US15/765,402 US10930931B2 (en) 2016-06-28 2017-06-28 Positive electrode active material for lithium secondary battery including high-voltage lithium cobalt oxide with doping element and method of preparing the same

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CN115440981A (zh) * 2022-08-26 2022-12-06 天津巴莫科技有限责任公司 正极活性材料及其制备方法、正极极片、二次电池和电子设备

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